The present invention relates to a heat-resistant rubber composition comprising an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber. More particularly, the invention relates to a vulcanizable heat-resistant rubber composition having high crosslinking efficiency given by an organic peroxide and capable of providing a vulcanized rubber molded product showing not only excellent mechanical and electrical properties but also prominently high thermal aging resistance, specifically a vulcanizable heat-resistant rubber composition having extremely good fluidity (molding processability).
Crosslinking of ethylene-xcex1-olefin copolymer rubbers is carried out using not sulfur, but organic,peroxides, because the copolymers have no double bond in their main chains. The rubbers have been used for automotive parts, industrial packing, electrical wires and electrical wire connecting parts, but these parts are desired to be produced at a low cost. For reducing the production cost, it is included to decrease an amount of an organic peroxide crosslinking agent. In these methods, however, the crosslinking is insufficiently performed, resulting in problems of low modulus and poor resistance to permanent set.
On the other hand, since ethylene-xcex1-olefin-nonconjugated diene copolymer rubbers prepared by copolymerizing ethylene, xcex1-olefins and nonconjugated polyenes have higher crosslinking efficiency given by an organic peroxides than ethylene-xcex1-olefin copolymer rubbers, the amount of the organic peroxide can be decreased. However, with respect to the ethylene-xcex1-olefin-nonconjugated diene copolymer rubber using 1,4-hexadiene, dicyclopentadiene or 5-ethylidene-2-norbornene as the nonconjugated diene, crosslinking is still insufficiently performed, and the thermal aging resistance is low because a large number of double bonds remain after the crosslinking reaction.
By the way, ethylene-propylene copolymer rubbers or ethylene-propylene-diene copolymer rubbers formed by a diene such as ethylidene norbornene, cyclopentadiene or 1,4-hexadiene have excellent mechanical and electrical properties. Moreover, they shows high thermal aging resistance and weathering resistance because they have no double bond in their main chains. Therefore, these rubbers have been widely used for automotive parts, industrial rubber parts, electrical parts and civil engineering and building materials, as described above. In the fields of automotive parts and electrical parts and the like, however, the ethylene-propylene copolymer rubbers and the ethylene-propylene-diene copolymer rubbers have been recently desired to have much higher thermal aging resistance and fluidity (molding processability).
In order to improve a fluidity of the ethylene-propylene copolymer rubbers, a method of adding oils as plasticizers to the copolymer rubbers is generally utilized. In the ethylene-propylene copolymer rubbers prepared utilizing this method, however, there reside problems that the thermal aging resistance of the molded product is lowered and an oil transfer phenomenon (i.e., bleeding) takes place to markedly reduce commercial values.
Further, a method of adding plastics such as polyethylene to the ethylene-propylene copolymer rubbers is also utilized to improve the fluidity. In the ethylene-propylene copolymer rubbers prepared utilizing this method, however, there generally reside problems of low heat resistance and poor elastomeric properties.
Furthermore, an ethylene copolymer rubber composition which is imparted with good processability (fluidity) by blending an ethylene-xcex1-olefin-polyene copolymer rubber having a different molecular weight is proposed in Japanese Patent Publication No. 14497/1984. However, this rubber composition does not show such high thermal aging resistance as desired.
On the other hand, some examples of conventional methods to improve the thermal aging resistance are described below.
(1) An anti-aging agent is added to the ethylene-propylene copolymer rubber or the ethylene-propylene-diene copolymer rubber.
(2) Since a breakage of a polymer main chain, as the heat deterioration reaction, easily takes place, an ethylene-propylene copolymer rubber which is softened after the heat deterioration and an ethylene-propylene-polyene copolymer rubber which is cured after the heat deterioration are blended.
(3) The diene content in the ethylene-propylene-polyene copolymer rubber is decreased.
A large number of combinations of these methods are also proposed.
For example, Japanese Patent Laid-Open Publication No. 23433/1985 proposes a rubber composition for sulfur vulcanization which is prepared by blending 100 parts by weight of an ethylene-xcex1-olefin-diene copolymer rubber having an iodine value of 5 to 12, 1 to 10 parts by weight of a phenol compound and 1 to 4 parts by weight of an imidazole compound.
The compositions proposed in the publication are improved in the thermal acing resistance, but the level thereof is not satisfactory in the uses for automotive parts and electrical parts, so that the thermal aging resistance should be much more improved.
In Japanese Patent Laid-Open Publication No. 108240/1989, a heat-resistant rubber composition comprising an ethylene-xcex1-olefin copolymer rubber, polyorganosiloxane and a silica type filler treated with a silane compound is disclosed as a heat-resistant rubber composition of high thermal aging resistance. The rubber composition disclosed in the publications are obviously improved in the thermal aging resistance, but the level thereof is not satisfactory in the uses for automotive parts and electrical parts, so that the thermal aging resistance should be much more improved. Moreover, these compositions do not show such high fluidity (molding processability) as desired.
Accordingly, development of a vulcanizable heat-resistant rubber composition having high crosslinking efficiency and capable of providing a vulcanized rubber molded product of high thermal aging resistance has been desired.
Further, development of a vulcanizable heat-resistant rubber composition capable of providing a vulcanized rubber molded product of prominently high thermal aging resistance without losing excellent mechanical and electrical properties inherent in the ethylene-propylene copolymer rubber or the ethylene-propylene-diene copolymer rubber has been also desired.
Furthermore, development of a vulcanizable heat-resistant rubber composition showing high fluidity (molding processability) and capable of providing a vulcanized rubber molded product of prominently high thermal aging resistance without losing excellent mechanical and electrical properties inherent in the ethylene-propylene copolymer rubber or the ethylene-propylene-diene copolymer rubber has been also desired.
The present invention is intended to solve such problems associated with the prior art as described above, and it is an object of the invention to provide a heat-resistant rubber composition being vulcanizable and having high crosslinking efficiency and capable of providing a vulcanized rubber molded product of high thermal aging resistance.
It is another object of the invention to provide a heat-resistant rubber composition being vulcanizable and capable of forming a vulcanized rubber molded product showing not only excellent mechanical and electrical properties but also prominently high thermal aging resistance.
It is a further object of the invention to provide a heat-resistant rubber composition being vulcanizable and having extremely good fluidity and capable of forming a vulcanized rubber molded product showing not only excellent mechanical and electrical properties but also prominently high thermal aging resistance.
A heat-resistant rubber composition according to the invention is a vulcanizable composition comprising:
an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) composed of ethylene, an xcex1-olefin of 3 to 20 carbon atoms and a nonconjugated polyene, and
an organic peroxide (B); and having vulcanizable properties,
said ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) having the following properties:
(1) a molar ratio of ethylene to the xcex1-olefin of 3 to 20 carbon atoms is in the range of 40/60 to 95/5 (ethylene/xcex1-olefin),
(2) the nonconjugated polyene is a vinyl end group-containing norbornene compound represented by the following formula [I]: 
xe2x80x83wherein R1 is a single bond or an alkenyl group of 2 to 10 carbon atoms, and R2 is hydrogen or an alkyl group of 1 to 5 carbon atoms,
(3) the nonconjugated polyene content is in the range of 0.5 to 50 g/100 g in terms of an iodine value, and
(4) an intrinsic viscosity [xcex7], as measured in decalin at 135xc2x0 C., of 0.1 to 10 dl/g.
The other heat-resistant rubber composition according to the invention is a vulcanizable composition comprising:
[I] an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) composed of ethylene, an xcex1-olefin of 3 to 20 carbon atoms and a nonconjugated polyene, in an amount of 100 parts by weight,
[II] an amine type anti-aging agent (C) composed of diphenylamines and/or phenylenediamines, in an amount of 0.2 to 5 parts by weight, and/or a hindered phenol type anti-aging agent (D) in an amount of 0.2 to 5 parts by weight,
[III] a sulfur type anti-aging agent (E) in an amount of 1 to 10 parts by weight, and
[IV] an organic peroxide (B);
said ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) having the following properties:
(1) a molar ratio of ethylene to the xcex1-olefin of 3 to 20 carbon atoms is in the range of 40/60 to 95/5 (ethylene/xcex1-olefin),
(2) the nonconjugated polyene is a vinyl end group-containing norbornene compound represented by the following formula [I]: 
xe2x80x83wherein R1 is a single bond or an alkenyl group of 2 to 10 carbon atoms, and R2 is hydrogen or an alkyl group of 1 to 5 carbon atoms,
(3) the nonconjugated polyene content is in the range of 0.5 to 50 g/100 g in terms of an iodine value, and
(4) an intrinsic viscosity [xcex7], as measured in decalin at 135xc2x0 C., of 0.1 to 10 dl/g.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) may be an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber having been graft-modified with an unsaturated carboxylic acid or its derivative.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) may be a blend of:
[I] an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) having an intrinsic viscosity [xcex7], as measured in decalin at 135xc2x0 C., of 1 to 10 dl/g, in an amount of 30 to 95 parts by weight, and
[II] an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2) having an intrinsic viscosity [xcex7], as measured in decalin at 135xc2x0 C., of 0.1 to 5 dl/g, this intrinsic viscosity being different from the intrinsic viscosity of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1), in an amount of 5 to 70 parts by weight,
the total amount of said components (A1) and (A2) being 100 parts by weight.
Each of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A1) and (A2) has the following properties:
(1) said copolymer rubber is a copolymer rubber composed of ethylene, an xcex1-olefin of 3 to 20 carbon atoms and a nonconjugated polyene,
(2) a molar ratio of ethylene to the xcex1-olefin of 3 to 20 carbon atoms is in the range of 40/60 to 95/5 (ethylene/xcex1-olefin),
(3) the nonconjugated polyene is a vinyl end group-containing norbornene compound represented by the above formula [I], and
(4) the nonconjugated polyene content is in the range of 0.5 to 50 g/100 g in terms of an iodine value.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) which is a blend of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) and the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2) has:
(i) a Mooney viscosity [ML1+4(100xc2x0 C.)] of 5 to 180,
(ii) a molar ratio of ethylene to the xcex1-olefin of 40/60 to 95/5 (ethylene/xcex1-olefin), and
(iii) a nonconjugated polyene content of 0.5 to 50 g/100 g in terms of an iodine value.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) and/or the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2) may be an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber having been graft-modified with an unsaturated carboxylic acid or its derivative.
When the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) which is a blend of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) and the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2) is used, a vulcanizable heat-resistant rubber composition having extremely good fluidity and capable of forming a vulcanized rubber molded product showing not only excellent mechanical and electrical properties but also prominently high thermal aging resistance and high crosslinking efficiency can be obtained.
A heat-resistant rubber composition according to the invention is described in detail hereinafter.
A heat-resistant rubber composition according to the invention is a vulcanizable rubber composition comprising:
an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) and an organic peroxide (B).
The other heat resistant rubber composition of the invention according to the invention is a vulcanizable rubber composition comprising:
[I] an ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A),
[II] an amine type anti-aging agent (C) and/or a hindered phenol type anti-aging agent (D),
[III] a sulfur type anti-aging agent (E), and
[IV] an organic peroxide (B).
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) is a rubber prepared by copolymerizing ethylene, an xcex1-olefin of 3 to 20 carbon atoms and a nonconjugated polyene.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) may be a blend of ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A1) and (A2) each of which is by copolymerizing ethylene, an xcex1-olefin of 3 to 20 carbon atoms and a nonconjugated polyene.
Examples of the xcex1-olefins of 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene. These xcex1-olefins are used singly or in combination of two or more kinds.
Of the above xcex1-olefins, preferred are propylene, 1-butene, 1-hexene, 1-octene and 1-decene.
In the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A), (A1) and (A2), a molar ratio of ethylene to the xcex1-olefin of 3 to 20 carbon atoms is in the range of 40/60 to 95/5 (ethylene/xcex1-olefin), preferably 50/50 to 90/10, more preferably 55/45 to 85/15, particularly preferably 55/45 to 80/20.
The nonconjugated polyene is a vinyl end group-containing cyclic diene compound and is a vinyl end group-containing norbornene compound represented by the following formula [I]. 
In the formula [I], R1 is a single bond or an alkenyl group of 2 to 10 carbon atoms.
The terms xe2x80x9cR1 is a single bondxe2x80x9d mean that the carbon atom for forming the norbornene ring and the carbon atom of the vinyl group are not via the group R1 but directly bonded.
Examples of the alkenyl groups of 2 to 10 carbon atoms indicated by R1 include ethynyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and decenyl.
R2 is hydrogen or an alkyl group of 1 to 5 carbon atoms.
Examples of the alkyl groups of 1 to 5 carbon atoms indicated by R2 include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl and neopentyl.
Examples of the vinyl end group-containing norbornene compounds represented by the formula [I] include 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene and 5-methylene-2-norbornene. Of these, preferred are 5-vinyl-2-norbornene and 5-methylene-2-norbornene.
Also employable as the nonconjugated polyene is a chain diene compound containing vinyl groups at the both ends, which is represented by the following formula [II]. 
In the formula [II], R1 is identical with R1 in the formula [I], and R2 and R3 are each identical with R2 in the formula [I].
The nonconjugated polyene compounds represented by the formulas [I] and [II] can be used singly or in combination of two or more kinds. Further, the nonconjugated polyene compounds represented by the formulas [I] and [II] can be used in combination with the following nonconjugated polyene compounds:
chain nonconjugated diene compounds, such as 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene and 7-methyl-1,6-octadiene;
cyclic nonconjugated diene compounds, such as methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene; and
triene compounds, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) used in the invention has a nonconjugated polyene content of 0.5 to 50, preferably 1 to 40 in terms of an iodine value.
When the nonconjugated polyene content is less than 0.5 in terms of an iodine value, the crosslinking efficiency is lowered. When the nonconjugated polyene content exceeds 50, the resulting rubber composition has poor resistance to environmental deterioration.
The nonconjugated polyene content is an indication of a vulcanizing rate in the vulcanization process. Together with other properties such as an intrinsic viscosity and an ethylene content, the nonconjugated polyene content contributes to the preparation of a copolymer rubber having good fluidity (molding processability) and high strength.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) used in the invention has an intrinsic viscosity [xcex7], as measured in decalin at 135xc2x0 C., of 0.1 to 10 dl/g, preferably 0.5 to 7 dl/g, more preferably 0.9 to 5 dl/g.
When the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) having an intrinsic viscosity within the above range is used, a rubber composition showing good fluidity (molding processability) and capable of providing a vulcanized rubber of excellent properties can be obtained.
The intrinsic viscosity [xcex7] is an indication of a molecular weight of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A). Together with other properties such as the nonconjugated polyene content, the intrinsic viscosity contributes to the preparation of a copolymer rubber having excellent fluidity (molding processability), strength, heat resistance and weathering resistance.
In the blend of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A1) and (A2), that is used as the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), each of the copolymer rubbers (A1) and (A2) has a nonconjugated polyene content of 0.5 to 50, preferably 1 to 40 in terms of an iodine value.
When the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A1) and (A2) having a nonconjugated polyene content within the above range are used, a rubber composition capable of providing a vulcanized rubber molded product of prominently high thermal aging resistance can be obtained.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) has an intrinsic viscosity [xcex7], as measured in decalin at 135xc2x0 C., of 1 to 10 dl/g, preferably 2 to 6 dl/g, more preferably 3 to 5 dl/g.
When the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) having an intrinsic viscosity within the above range is used, a rubber composition showing good fluidity (molding processability) and capable of providing a vulcanized rubber of excellent properties can be obtained.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2) has an intrinsic viscosity [xcex7], as measured in decalin at 135xc2x0 C., of 0.1 to 5 dl/g, preferably 0.2 to 2 dl/g, more preferably 0.3 to 1 dl/g.
By blending the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2) having an intrinsic viscosity within the above range and the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1), a rubber composition showing good fluidity (molding processability) and capable of providing a vulcanized rubber of excellent properties can be obtained.
The blend of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A1) and (A2) has a Mooney viscosity (ML1+4(100xc2x0 C.) of 5 to 180, a molar ratio of ethylene to the xcex1-olefin of 40/60 to 95/5 (ethylene/xcex1-olefin), and a polyene content of 0.5 to 50 in terms of an iodine value.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A), (A1) and (A2) can be prepared by processes described in, for example, Japanese Patent Publication No. 14497/1984. That is, the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A), (A1) and (A2) can be obtained by copolymerizing ethylene, the xcex1-olefin of 3 to 20 carbon atoms and the nonconjugated polyene in the presence of Ziegler catalyst using hydrogen as a molecular weight modifier.
The ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A), (A1) and (A2) may be graft-modified products obtained by graft-modifying the above-described ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers with unsaturated carboxylic acids or their derivatives (acid anhydrides, esters).
Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid and bicyclo(2,2,1)hepto-2-ene-5,6-dicarboxylic acid.
Examples of the unsaturated carboxylic anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride and bicyclo(2,2,1)hepto-2-ene-5,6-dicarboxylic anhydride.
Of these, preferred is maleic acid.
Examples of the unsaturated carboxylic esters include methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate and dimethyl bi(cyclo(2,2,1)hepto-2-ene-5,6-dicarboxylate. Of these, preferred are methyl acrylate and ethyl acrylate.
The graft modifiers (graft monomers) such as the unsaturated carboxylic acids are used singly or in combination of two or more kinds. In any case, the graft quantity is preferably not more than 0.1 mol based on 100 g of the aforementioned unmodified ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber.
When the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A), (A1) and (A2) having a graft quantity within the above range are used, a rubber composition showing good fluidity (molding processability) and capable of providing a vulcanized rubber molded product of excellent low-temperature resistance can be obtained.
The graft-modified ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber can be obtained by causing the unmodified ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber to react with the unsaturated carboxylic acid or its derivative in the presence of a radical initiator.
This graft reaction can be carried out in a solution state or a molten state. When the graft reaction is performed in the molten state, it is most efficient and preferred to continuously perform the reaction in an extruder.
Examples of the radical initiators used for the graft reaction include:
dialkyl peroxides, such as dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxyne)hexyne-3,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-mono(t-butylperoxy)hexane and xcex1,xcex1xe2x80x2-bis (t-butylperoxy-m-isopropyl)benzene;
peroxy esters, such as t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate and di-t-butyl peroxyphthalate;
ketone peroxides, such as dicylohexanone peroxide; and
mixtures of these compounds.
Of these, preferred are organic peroxides having a temperature, at which the half-life period thereof corresponds to one minute, of 130 to 200xc2x0 C., and among them particularly preferred are dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide and t-butyl hydroperoxide.
In the present invention, the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A), (A1) and (A2) having a Mooney viscosity [ML1+4(100xc2x0 C.)] of 5 to 180, particularly 10 to 120, are preferably used from the viewpoints of mechanical properties and fluidity (molding processability).
In the blend of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) and the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2), that is used as the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) is used in an amount of 30 to 95 parts by weight, preferably 35 to 80 parts by weight, more preferably 40 to 70 parts by weight, based on 100 parts by weight of the total amount of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) and the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2); and the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2) is used in an amount of 5 to 70 parts by weight, preferably 10 to 65 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the total amount of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A1) and the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A2).
The organic peroxide used in the invention is an organic peroxide which is conventionally used for rubbers.
Examples of the organic peroxides include:
dialkyl peroxides, such as dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxyne)hexyne-3,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-mono(t-butylperoxy)hexane and xcex1,xcex1xe2x80x2-bis(t-butylperoxy-m-isopropyl)benzene;
peroxy esters, such as t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butylperoxymaleic acid, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate and di-t-butyl peroxyphthalate;
ketone peroxides, such as dicyclohexanone peroxide; and
mixtures of these compounds.
Of these, preferred are organic peroxides having a temperature, at which the half-life period thereof corresponds to one minute, of 130 to 200xc2x0 C., and among them, particularly preferred are dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide and t-butyl hydroperoxide.
The organic peroxide is used in an amount of 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol, based on 100 g of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), but it is desired that the optimum amount is properly determined according the required property values.
When the organic peroxide is used as a vulcanizing agent, a vulcanization aid is preferably used inxe2x80x94combination. Examples of the vulcanization aids include sulfur; quinonedioxime compounds, such as p-quinonedioxime; methacrylate compounds, such as polyethylene glycol dimethacrylate; allyl compounds, such as diallyl phthalate and triallyl cyanurate; maleimide compounds; and divinylbenzene. The vulcanization aid is used in an amount of 0.5 to 2 mol based on 1 mol of the organic peroxide, preferably in an equimolar amount.
In the present invention, diphenylamines and/or phenylenediamines are used as the amine type anti-aging agent (C).
Examples of the diphenylamines include p-(p-toluenesulfonylamide)-diphenylamine, 4,4xe2x80x2-(xcex1,xcex1xe2x80x2dimethylbenzyl)diphenylamine, 4,4xe2x80x2-dioctyldiphenylamine, a high-temperature reaction product of diphenylamine and acetone, a low-temperature reaction product of diphenylamine and acetone, a low-temperature reaction product of diphenylamine, aniline and acetone, a reaction product of diphenylamine and diisobutylene, octylated diphenylamine, dioctylated diphenylamine, p,pxe2x80x2-dioctyldiphenylamine and alkylated diphenylamine.
Examples of the phenylenediamines include p-phenylenediamines, such as N,Nxe2x80x2-diphenyl-p-phenylenediamine, n-isopropyl-Nxe2x80x2-phenyl-p-phenylenediamine, N,Nxe2x80x2-di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-Nxe2x80x2-phenyl-p-phenylenediamine, N-phenyl-Nxe2x80x2-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-methylheptyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N-bis(1,3-dimethylbutyl)-Nxe2x80x2-phenyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine and phenyloctyl-p-phenylenediamine.
Of these, particularly preferred are 4,4xe2x80x2-(xcex1,xcex1xe2x80x2dimethylbenzyl)diphenylamine and N,Nxe2x80x2-di-2-naphthyl-p-phenylenediamine.
These compounds can be used singly or in combination of two or more kinds.
In the present invention, the amine type anti-aging agent (C) is used in an amount of 0.2 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A). When the amine type anti-aging agent (C) is used in the above-mentioned amount, the thermal aging resistance can be highly improved, and crosslinking of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) is not inhibited.
Examples of the hindered phenol type anti-aging agents (D) include:
(1) 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenylbutane),
(2) 4,4xe2x80x2-butylidene-bis(3-methyl-6-t-butylphenol),
(3) 2,2-thiobis(4-methyl-6-t-butylphenol),
(4) 7-octadecyl-3-(4xe2x80x2-hydroxy-3xe2x80x2,5xe2x80x2-di-t-butylphenyl)propionate,
(5) tetrakis[methylene-3-(3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxyphenyl)propionate]methane,
(6) pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
(7) triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
(8) 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
(9) 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,
(10) tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate,
(11) 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
(12) N,Nxe2x80x2-hexamethylenebis(3,5-di-t-butyl-4-hydroxy)hydrocinnmamide,
(13) 2,4-bis[(octylthio)methyl]-o-cresol,
(14) 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester
(15) tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane,
(16) octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and
(17) 3,9-bis[2-{3(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4-8,10-tetraoxaspiro[5,5]undecane.
Of these, preferred are the above phenol compounds (5) and (17).
In the present invention, the hindered phenol type anti-aging agent (D) is used in an amount of 0.2 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A). When the hindered phenol type anti-aging agent (D) is used in the above-mentioned amount, the thermal aging resistance can be highly improved, and crosslinking of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) is not inhibited.
The sulfur type anti-aging agent (E) used in the invention is a sulfur type anti-aging agent which is conventionally used for rubbers.
Examples of the sulfur type anti-aging agents (E) include those of imidazole type, such as 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole and zinc salt of 2-mercaptomethylbenzimidazole; and those of aliphatic thioether type, such as dimyristyl thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate and ditridecyl thiodipropionate, pentaerythritol-tetrakis-(xcex2-lauryl-thiopropionate). Of these, particularly preferred are 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole and pentaerythritol-tetrakis-(xcex2-lauryl-thiopropionate).
In the present invention, the sulfur type anti-aging agent (E) is used in an amount of 1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 1 to 6 parts by weight, based on 100 parts by weight of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A). When the sulfur type anti-aging agent (E) is used in the above-mentioned amount, the thermal aging resistance can be highly improved, and crosslinking of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) is not inhibited.
The heat-resistant rubber composition according to the invention can be used in an unvulcanized state, but when it is used in the form of a vulcanized product such as a vulcanized rubber molded product or a vulcanized rubber foamed product, its properties are most conspicuously exhibited.
To the heat-resistant rubber composition of the invention, known additives such as rubber reinforcement, softener, vulcanization aid, processing aid, foaming agent, foaming aid, colorant, dispersant and flame retardant can be added according to the use of the aimed vulcanized product, in addition to the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), the organic peroxide (B), if necessary, the amine type anti-aging agent (C) and/or the hindered phenol type anti-aging agent (E), and the sulfur type anti-aging agent (E).
The total amount of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), the amine type anti-aging agent (C), the hindered phenol type anti-aging agent (D) and the sulfur type anti-aging agent (E) in the rubber composition is usually not less than 25% by weight, preferably not less than 40% by weight, though it varies depending on the uses.
The rubber reinforcement serves to enhance mechanical properties such as tensile strength, tear strength and abrasion resistance of the vulcanized rubber. Examples of the rubber reinforcements include carbon black such as SRF, GPF, FEF, MAE, HAF, ISAF, SAF, FT and MT, carbon black thereof which are surface-treated with, for example, silane coupling agents, silica, activated calcium carbonate, powdery talc and powdery silicic acid.
Though the amount of the rubber reinforcement can be selected according to the use of the vulcanized rubber, but the amount thereof is usually not more than 200 parts by weight, particularly not more than 100 parts by weight, based on 100 parts by weight of the total amount of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), the amine type anti-aging agent (C), the hindered phenol type anti-aging agent (D) and the sulfur type anti-aging agent (E).
As the softeners, those conventionally used for rubbers are employable, and examples thereof include:
petroleum type softening agents, such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and vaseline;
coal tar type softeners, such as coal tar and coal tar pitch;
fatty oil type softeners, such as castor oil, linseed oil, rapeseed oil and coconut oil;
tall oil;
factice;
waxes, such as beeswax, carnauba wax and lanolin;
fatty acids and fatty acid salts, such as ricinolic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; and
synthetic polymer materials, such as petroleum resin, atactic polypropylene and coumarone-indene resin.
Of these, preferred are petroleum type softeners, and among them, particularly preferred is process oil.
Though the amount of the softener can be selected according to the use of the vulcanized rubber, but the amount thereof is usually not more than 200 parts by weight, particularly not more than 100 parts by weight, based on 100 parts by weight of the total amount of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), the amine type anti-aging agent (C), the hindered phenol type anti-aging agent (D) and the sulfur type anti-aging agent (E).
When electron rays are used for the vulcanization instead of using the vulcanizing agent, the unvulcanized compounded rubber is irradiated with the electron rays having energy of 0.1 to 10 MeV (megaelectron volt), preferably 0.3 to 2 MeV, in such a manner that the absorbed dose becomes 0.5 to 35 Mrad (megarad), preferably 0.5 to 10 Mrad.
In this case, the vulcanization aid, that is used in combination with the organic peroxide (vulcanizing agent), may be used. The vulcanization aid is used in an amount of 0.0001 to 0.1 mol, preferably 0.001 to 0.03 mol, based on 100 g of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A).
As the processing aids, those conventionally used for rubbers are employable, and examples thereof include higher fatty acids, such as ricinolic acid, stearic acid, palmitic acid and lauric acid; salts of higher fatty acids, such as barium stearate, zinc stearate and calcium stearate; and esters of higher fatty acids, such as recinolic acid ester, stearic acid ester, palmitic acid ester and lauric acid ester.
The processing aid is used in an amount of not more than 10 parts by weight, preferably not more than 5 parts by weight, based on 100 parts by weight of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), but it is desired that the optimum amount is properly determined according the required property values.
Examples of the foaming agents include:
inorganic foaming agents, such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate and ammonium nitrite;
nitroso compounds, such as N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-dinitrosoterephthalamide and N,Nxe2x80x2-dinitrosopentamethylenetetramine;
azo compounds, such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene and barium azodicarboxylate;
sulfonylhydrazide compounds, such as benzenesulfonylhydrazide, toluenesulfonylhydrazide, p,pxe2x80x2-oxybis(benzenesulfonylhydrazide) and diphenylsulfone-3,3xe2x80x2-disulfonylhydrazide; and
azide compounds, such as calcium azide, 4,4-diphenyldisulfonylazide and p-toluenesulfonylazide.
The foaming agent is used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A). When the foaming agent is used in the above-mentioned amount, a foamed product having an apparent specific gravity of 0.03 to 0.8 g/cm3 can be obtained. However, it is desired that the optimum amount is properly determined according the required property values.
A foaming aid may be used in combination with the foaming agent, if desired. The foaming aid has functions of lowering a decomposition temperature of the foaming agent, acceleration of decomposition and production of uniform foam.
Examples of the foaming aids include organic acids, such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and its derivative.
The foaming aid is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), but it is desired that the optimum amount is properly determined according the required property values.
As described hereinbefore, the heat-resistant rubber composition of the invention can be used in the unvulcanized state, but when it is used in the form of a vulcanized product such as a vulcanized rubber molded product or a vulcanized rubber foamed product, its properties are most conspicuously exhibited.
For preparing a vulcanizate from the heat-resistant rubber composition of the invention, an unvulcanized compounded rubber is first prepared, then the compounded rubber is molded into a product of desired shape, and the product is vulcanized, similarly to a method of vulcanizing conventional rubbers.
For the vulcanization, any of a heating method using a vulcanizing agent and an electron ray-irradiation method may be adopted.
The heat-resistant rubber composition of the invention can be prepared by, for example, the following process.
That is, the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), and if necessary, additives such as filler and softener are kneaded at 80 to 170xc2x0 C. for 3 to 10 minutes using internal mixers (closed type mixers) such as Banbury mixer, kneader and intermixer; then the organic peroxide (vulcanizing agent), and if necessary, the vulcanization aid and the foaming agent are added; and the resulting mixture is kneaded at a roll temperature of 40 to 80xc2x0 C. for 5 to 30 minutes using rolls (e.g., open rolls) or kneaders, followed by rolling.
The heat-resistant rubber composition of the invention comprising the anti-aging agent can be prepared by kneading the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), the amine type anti-aging agent (C), the hindered phenol type anti-aging agent (D), the sulfur type anti-aging agent (E), and if necessary, additives such as filler and softener at 80 to 170xc2x0 C. for 3 to 10 minutes using internal mixers (closed type mixers) such as Banbury mixer, kneader or intermixer; then adding the organic peroxide (B) (vulcanizing agent), and if necessary, the vulcanization aid and the foaming agent; and kneading the resulting mixture at a roll temperature of 40 to 80xc2x0 C. for 5 to 30 minutes using rolls (e.g., open rolls) or kneaders, followed by rolling.
If the kneading temperature of the internal mixer is low, the anti-aging agents (C), (D) and (E), the vulcanizing agent, and other additives such as colorant, dispersant, flame retardant and foaming agent may be kneaded together with the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) and additives such as filler and softener.
The vulcanizable heat-resistant rubber composition of the invention obtained as above is molded into a desired shape using various means such as an extrusion molding machine, a calender roll, a press, an injection molding machine or a transfer molding machine, and simultaneously or thereafter the molded product is heated at a temperature of 120 to 270xc2x0 C. for 1 to 30 minutes in a vulcanizing bath to perform vulcanization. Or, the vulcanized product can be obtained by irradiation to it with electron rays in the aforesaid manner. In the vulcanization, a mold may be used or may not be used. When a mold is not used, the vulcanization is generally carried out continuously. The heating in the vulcanizing bath can be performed by the use of heating means such as hot air, glass bead fluidized bed, UHF (ultrahigh frequency electromagnetic wave), steam or LCM (molten salt bath). In the vulcanization using irradiation with electron rays, a compounded rubber containing no vulcanizing agent is used.
A heat-resistant rubber composition of the invention comprises the specific ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) and the organic peroxide (B). Therefore, the composition has high crosslinking efficiency and a high modulus, and can provide a vulcanized rubber molded product having excellent resistance to environmental deterioration such as thermal aging resistance.
The other heat-resistant rubber composition of the invention comprises the specific ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A), the amine type anti-aging agent (C) and/or the hindered phenol type anti-aging agent (E), the sulfur type anti-aging agent (E) and the organic peroxide (B). Therefore, the composition can provide a vulcanized rubber molded product showing not only excellent mechanical and electrical properties but also prominently high thermal aging resistance. These effects can be obtained by the use of a combination of the amine type anti-aging agent (C) and the sulfur type anti-aging agent (E), a combination of the hindered phenol type anti-aging agent (D) and the sulfur type anti-aging agent (E), or a combination of the amine type anti-aging agent (C), the hindered phenol type anti-aging agent (D) and the sulfur type anti-aging agent (E).
Among the heat-resistant composition of the invention, a composition comprising ethylene-xcex1-olefin-nonconjugated polyene copolymer rubber (A) containing a blend of specific amounts of the ethylene-xcex1-olefin-nonconjugated polyene copolymer rubbers (A1) and (A2) having different intrinsic viscosities (i.e., having different molecular weights) particularly has extremely good fluidity (molding processability) and can provide a vulcanized rubber molded product showing not only excellent mechanical and electrical properties but also prominently high thermal aging resistance.
Accordingly, the heat-resistant rubber composition which exerts such effects as mentioned above can be favorably used for automotive parts such as weatherstrip, door glass run channel, window frame, radiator hose, brake parts and wiper blade; industrial rubber parts such as rubber roll, belt, packing and hose; electrical insulating materials such as anode cap and grommet; and building materials such as building gasket.